Resolution of structures and structural dynamics for catalysts at active electrode interfaces is necessary to resolve mechanisms for function and assembly in solar fuels applications. We have been developing porous, high-surface area, low X-ray background, 3-D electrodes for interfacial structural analysis of molecular and amorphous metal oxide water-splitting catalysts using X-ray scattering and atomic pair distribution function (PDF) analysis. We demonstrate the opportunity to use ALD-ITO coated microchannel plates and other micro- to nano-porous substrates for characterization of domain structures for amorphous metal oxides water-oxidation catalysts used in artificial leaf assemblies. This presentation will compare domain structures resolved for amorphous cobalt oxide films formed electrolytically as a function of ligand and electrolyte anion variation. For cobalt oxide catalysts, the results show that phosphate is unique in restricting domain size to small, single-layer domains where defects and edge distortions can be resolved. The results show that catalytic currents for do not scale with the domain edge content in the cobaltate films, which are the presumed sites for water oxidation catalysis, but instead track the extend of domain layering and conductivity properties of the films. These results support the view that overall catalytic activity in amorphous cobaltate thin films is determined by the charge accumulation and transport properties.  We have extended these techniques demonstrate the opportunity to measure PDF for homogeneous water oxidation catalysts. PDF measurements with 0.2 Å spatial resolution are found to be sufficient to resolve redox and catalytic state dependent changes in ligand structure.  This work establishes a foundation for extending the X-ray PDF method for the analysis of atomic structure changes in molecular catalysts driven by excited-state, sequential single electron photo-chemistry.